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Organic vapor phase deposition for the growth of large area organic electronic devices Richard R.

Organic vapor phase deposition for the growth of large area organic electronic devices

Citation: Appl. Phys. Lett. 95, 233305 (2009); doi: 10.1063/1.3271797

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Richard R. Lunt,


Brian E. Lassiter, Jay B. Benziger, and Stephen R. Forrest 1, a



1 Department of Electrical Engineering and Computer Science, Department of Physics, and Department of Materials Science and Engineering, University of Michigan, Ann Arbor, Michigan 48109 USA 2 Department of Chemical Engineering, Princeton Institute for the Science and Technology of Materials (PRISM), Princeton University, Princeton, New Jersey 08544 USA

Received 7 August 2009; accepted 13 November 2009; published online 11 December 2009

We demonstrate that material utilization efficiencies of 50% and deposition nonuniformities 2.5% are achievable over substrate diameters of 200 mm using a simplified, organic vapor phase deposition OVPD system. The OVPD system is used to demonstrate doped electrophosphorescent organic light emitting diodes whose performance is comparable to those grown by vacuum thermal evaporation. Through continuum modeling, we demonstrate that analogous systems whose chamber dimensions are comparable to the substrate width are scalable to substrate sizes of at least 1500 1800 mm 2 with deposition nonuniformities between 1.5% and 2.5%. These results indicate that OVPD is useful in the large area deposition of displays, lighting, and other organic electronic devices. © 2009 American Institute of Physics. doi:10.1063/1.3271797

Organic vapor phase deposition OVPD has been dem- onstrated to be an effective deposition technology for high-

performance thin-film organic photovoltaics,

and light emitting diodes OLEDs .

materials are thermally evaporated into an inert carrier gas stream that transports the molecules through a heated cham- ber. There, diffusive mixing generates a uniform organic flux that is physisorbed onto a cooled substrate. 9 , 10 The hot-

walled reactor avoids unwanted deposition on its surfaces, leading to efficient materials usage and reduced system down-time for cleaning. Preliminary studies on scaling to 400 400 mm 2 Gen -2 substrates through the use of a

complex and potentially costly closed-coupled showerhead for materials distribution over large substrate areas have re- cently been reported. 11 Here, we investigate the scalability of a simplified OVPD chamber design to sizes that can accommodate 200

mm diameter substrates based on both experiment and simu-

lation. We explore the possibility of scaling to even larger,

Gen-6 1500 1800 mm 2 size substrates. We show that a

simple flow distribution system can produce both film thick- ness uniformity and morphological control over large areas while avoiding the use of complex material distributors con- nected by lengthy organic source feed lines that can hinder scaling of the technology to very large substrates. 7 , 12 Using a prototype, automated, mid-size OVPD chamber that ac- commodates 200 mm diameter wafers, we show that material usage efficiencies of 50% with variations in film thickness 2.5% are achievable. With this system, we demonstrate the growth of green electrophosphorescent OLEDs PHOLEDs that exhibit performance comparable to those grown by vacuum thermal evaporation VTE . Based on these experi- ments, continuum fluid dynamics modeling is used to inves- tigate the scaling of OVPD to at least Gen-6 size substrates.

Our results suggest that OVPD is scalable to very large sub-

strates, making it a key growth technology for low-cost or-

ganic electronics.

In OVPD, organic


, 2






a Electronic mail:

The computer-automated vertical OVPD system 13 con- sists of ten source plenums mounted radially along one end

of a 250 mm diameter deposition chamber see Fig. 1 . Each

source is individually loaded into a 5 cm 3 alumina source crucible. The crucible is linearly translated within a tempera- ture gradient to generate a range of organic partial pressures. A plug-valve is used to shutter the organic flux entering the reactor vessel from the deposition plenum. 2 Flux from each source is directed toward a cooled 260–370 K substrate holder. The deposition chamber also acts as a diffusive- mixing zone for organic dopants and hosts, eliminating the

need for a material distributor.

The system is equipped with


for a material distributor. The system is equipped with 12 FIG. 1. Color a Cross-section schematic

FIG. 1. Color a Cross-section schematic of the experimental mid-scale OVPD system. The reactor chamber diameter is 250 mm. b Cross-section of the deposition source plenum. The source crucible is linearly translated along a temperature gradient heater to control organic source partial pressure.

0003-6951/2009/95 23 /233305/3/$25.00

95 , 233305-1

© 2009 American Institute of Physics

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Lunt et al.

233305-2 Lunt et al. FIG. 2. Color a Measured data points and calculated lines material utilization

FIG. 2. Color a Measured data points and calculated lines material utilization efficiency M for Alq 3 growth in the automated OVPD system as a function of total flow rate Q at pressure P = 1 Torr, and as a function of P at Q = 200 SCCM. Also shown is the deposition thickness profiles of 100 nm thick films of Alq 3 grown on a 200 mm Si wafer at P = 300 mTorr and Q = 100 SCCM top, right axes . The experimental unifor- mity of the Alq 3 film is 2.3% with rotation, and 5.0% without rotation. b Forward viewing external quantum symbols and luminous power effi- ciency lines of OVPD and VTE grown, green emitting Ir ppy 3 PHOLEDs. Devices with 0.785 mm 2 active area grown by OVPD circle, solid line and by VTE triangle, short dash ; device with 100 mm 2 active area inset grown by OVPD square, dash-dot .

a shutter positioned over the substrate, a quartz crystal film- thickness monitor, a pressure-regulating butterfly valve, and

a trolley system for in vacuo substrate transfer to a VTE

chamber for deposition of metal cathodes. Film thickness


troscopic ellipsometer. The uniformity of the deposition is calculated as the standard deviation of the thickness divided by the average thickness. Using the prototype, multisource OVPD system, the ma- terial utilization efficiency M and deposition uniformity were measured for the archetype molecular solid tris- 8- hydroxyquinoline aluminum Alq 3 grown on 200 mm di- ameter Si wafers for a range of conditions, as shown in Fig.

were performed using a variable-angle spec-


2 a . It was found that M varies only weakly with back- ground pressure P , but is more strongly dependant on the total deposition flow rate Q , as expected. As flow rate in- creases, both M and uniformity decrease due to an increase in convective transport that bypasses the substrate. Although the chamber pressure has only a small effect on M under equilibrium source conditions, it was found that higher pres-

sures improved the deposition uniformity as the source ve- locities are decreased, consistent with the uniformity depen- dence on the total source flow rate. Also shown in Fig. 2 a are the uniformities across 200


wafers, with and without rotation for a source flowrate


pressure of Q = 50 SCCM SCCM denotes standard cu-

bic centimeter per minute and P = 250 mtorr, respectively.

Appl. Phys. Lett. 95 , 233305 2009

Without rotation the deposition nonuniformity is 5.0%, which is nearly identical to the simulated nonuniformity of 5.1%. Alternatively, the uniformity improves to 2.3% with rotation. These nonuniformities stem primarily from flow- induced boundary-layer thinning near the sharp edge of the substrate that increases the diffusive flux and hence material build up. The uniformity can be improved by extending the substrate holder several centimeters beyond the substrate edge, increasing the diameter of the substrate chamber to significantly larger than the substrate itself or redirecting the outlet flow orthogonal to the substrate see below . To determine the quality of the films, high efficiency green electrophoshporescent OLEDs or PHOLEDs were deposited on an indium tin oxide coated glass substrate in the following sequence: 15 40 nm thick N,N -diphenyl-N,N -bis 1-naphthyl -1, 1 biphenyl-4, 4 diamine -NPD hole transporting layer, 20 nm thick 4 -bis 9-carbazolyl -2, 2 -biphenyl CBP host layer doped with 6% by volume of tris- 2-phenylpyridine iridium Ir ppy 3 , 10 nm thick bathocuproine BCP exciton and

hole blocking layer, 20 nm thick Alq 3 electron transport layer, and a LiF 0.8 nm /Al 100 nm cathode deposited through a shadow mask. All the organics layers were grown via OVPD except the control device at a rate of 0.1–0.25 nm/s with rotation. The chamber temperature was 573 K, and the source temperatures for NPD 0.2 nm/s , CBP 0.25 nm/

s , Ir ppy 3 0.02 nm/s , BCP 0.2 nm/s , and Alq 3 0.2 nm/s were 538, 535, 523, 455, and 543 K, respectively, with a source flow of 50 SCCM, total flow rate of 150 SCCM, background pressure of 500 mTorr, and a substrate tempera- ture of 300 K. Control devices with a similar structure were grown via VTE in a chamber with a base pressure of 10 6 Torr. The PHOLEDs were tested in air using standard procedures. 16 A comparison between the performance of VTE and OVPD-grown PHOLEDs is shown in Fig. 2 b . The 1 mm diameter OVPD and VTE devices are found to have similar peak forward viewing external quantum and power efficien- cies of 9.0% 0.3% and 21.0 1.2 lm / W, and 8.8% 0.4% and 24.2 1.5 lm / W, respectively. Similar devices grown by OVPD with a larger active area of 100 mm 2 show nearly identical efficiencies of 9.3% 0.5% and 23.8 1.5 lm / W. To understand the effects of scaling this system to even larger substrates, a continuum dynamics model was used to simulate the experimentally measured characteristics of the 250 mm diameter system. These simulations were then ex- tended to a Gen-6 OVPD system with Cartesian symmetry. 17 The continuum model of coupled energy, mass, and momen- tum Navier–Stokes balances was solved for the velocity, temperature, concentration flux , and pressure fields. The fluid density gradient was assumed to be weakly varying, allowing us to model the fluid as pseudocompressible: den- sity gradients are ignored in the continuity equation but the density is allowed to vary as an ideal gas. The flow field is, therefore, assumed to be only a function of the carrier gas i.e., dilute organic concentration . The temperature depen- dant viscosity and thermal conductivity of the nitrogen carrier gas used are = 1.73 10 5 T / 300 K kg / m s and k = 0.025 T / 300 K W / m K, respectively, 18 where T is the local temperature in Kelvin. The diffusivity is

calculated according

to D = D o T 3 / 2 / P , where D 0 = 5.2

10 5 m 2 Pa / s K 3 / 2 is obtained for Alq 3 using the kinetic


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Lunt et al.

233305-3 Lunt et al. FIG. 3. Color a Schematic of the continuum model simulations of a

FIG. 3. Color a Schematic of the continuum model simulations of a Gen-6 OVPD deposition tool along with the simulation mesh. b Simulated velocity and diffusive flux fields for pressure, P = 250 mTorr, carrier gas flow rate, Q = 1000 SCCM, and chamber length to width ratio, L / W = 1.0. c Simulated deposition uniformity as a function of flow rate Q in SCCM

and chamber dimensions L / W for W = 1.8 m lines are guides to the eye . d Series of deposition profiles as a function of flow rate Q in sccm at

P = 250 mTorr, L = 1.8 m and W = 1.8 m. With increasing flow

deposition profile approaches Gaussian as the flow-stream becomes jetlike.

rate, the

theory of gases, and P is the chamber pressure. The inlet organic concentration was fixed, 10 and the concentration at the cooled substrate nonrotating was assumed to be 0 cor- responding to a molecular sticking coefficient of 1 . A schematic of the simulated deposition chamber is shown in Fig. 3 a . Simulation results for the carrier velocity and diffusive flux are plotted in Fig. 3 b for an inlet volu- metric flowrate of Q = 1000 SCCM, a chamber temperature of 600 K, substrate temperature of 300 K, background pres- sure P = 250 mTorr, chamber length and width of L = W = 1.8 m, respectively, inlet diameter of 0.2 m, exhaust ports of 0.2 m, and substrate size of 1.5 m. As outlined elsewhere, 10 the simulated deposition rate is found to in- crease as Q and 1 / P under equilibrium source conditions. In Fig. 3 c , the uniformity in the Gen-6 chamber is plot- ted as a function of the chamber length-to-width ratio L / W for W = 1.8 m at a background pressure of 250 mTorr and a variety of source flow rates. The deposition profiles for one set of data at fixed chamber dimensions L / W = 1.0 are shown in Fig. 3 d . An optimal chamber ratio L / W = 0.75 is found to have 1.5%–2.5% thickness nonuniformity for a range of deposition conditions while also minimizing the chamber volume. The material utilization efficiency is found to be a weak function of L / W , and is primarily affected by the total flow rate, which dictates the degree of convective transport. The material usage efficiency, therefore, decreases with increasing flow rate similar to the experimental data shown in Fig. 2 , with M = 40 % at Q = 500 SCCM and L / W = 1. While an increase in the diffusivity leads to an in- crease in M , changes in D 0 have little effect. This suggests that the simulations semiquantitatively reflect our experi- mental results despite uncertainties in the magnitude of the input modeling parameters. For this configuration, inlet ve- locities 0.25 m / s are necessary to avoid the formation of

Appl. Phys. Lett. 95 , 233305 2009

natural convection eddies that can disrupt the flow pattern. Although not exhaustive, these simulations indicate that there are several chamber configurations, along with a range of operating conditions, that can lead to uniform deposition

profiles. In conclusion, we have demonstrated a simple OVPD deposition system that exhibits material usage efficiencies up to 41% 5 % and film uniformities of 2%–3% across 200

mm wafers without the need for showerheads or baffles.

These results are in agreement with continuum dynamics simulations. This indicates that the scale-up of this system can lead to large-area deposition thickness nonuniformities of only 1.5%–2.5% over Gen-6 substrates sizes. Addition-

ally, we have shown that PHOLEDs grown by VTE and

OVPD exhibit similar performance. This work demonstrates

the potential of OVPD as a method for the deposition of large-scale PHOLEDs for white lighting and displays, as

well as for a range of organic electronic applications.

The authors thank Dr. Fan Yang for assisting in the early stages of machine design, and David Pitts and Andrew Bass from Angstrom Engineering Kitchener, Ontario for their expert advice and construction of the OVPD system. We also thank the Department of Energy EERE Program, Universal Display Corp., and Global Photonic Energy Corp. for their support of this work.

1 F. Yang, M. Shtein, and S. R. Forrest, Nature Mater. 4, 37 2005 . 2 F. Yang, K. Sun, and S. R. Forrest, Adv. Mater. 19, 4166 2007 . 3 C. Rolin, S. Steudel, K. Myny, D. Cheyns, S. Verlaak, J. Genoe, and P.

Heremans, Appl. Phys. Lett. 89, 203502 2006 . 4 M. Shtein, J. Mapel, J. B. Benziger, and S. R. Forrest, Appl. Phys. Lett.

81 , 268 2002 .

5 M. A. Baldo, V. G. Kozlov, P. E. Burrows, S. R. Forrest, V. S. Ban, B. Koene, and M. E. Thompson, Appl. Phys. Lett. 71, 3033 1997 . 6 Y. R. Sun, M. Shtein, and S. R. Forrest, Appl. Phys. Lett. 86, 113504 2005 . 7 T. X. Zhou, T. Ngo, J. J. Brown, M. Shtein, and S. R. Forrest, Appl. Phys. Lett. 86, 021107 2005 . 8 M. Bösing, F. Zimmerman, F. Lindla, P. van Gemmen, D. Bertram, N. Meyer, D. Keiper, M. Heuken, H. Kalisch, and R. Jansen, Mater. Res. Soc. Symp. Proc. 1154, 1154 2009 . 9 M. Baldo, M. Deutsch, P. Burrows, H. Gossenberger, M. Gerstenberg, V. Ban, and S. Forrest, Adv. Mater. 10, 1505 1998 . 10 M. Shtein, H. F. Gossenberger, J. B. Benziger, and S. R. Forrest, J. Appl. Phys. 89, 1470 2001 . 11 B. Marheineke, Proc. SPIE 5961, 596101 2005 . 12 M. Schwambera, M. Gersdorff, N. Meyer, M. Reinhold, G. Strauch, M. Heuken, B. Marheineke, T. McEntee, S. Hartmann, W. Kowalsky, C. Him- cinshi, and D. Zahn, Proceedings of the 8th Asian Symposium on Infor- mation Display ASID’04 , 2004 , p. 370. 13 System assembled by Angstrom Engineering. 14 Material utilization efficiency was calculated as the mass deposited on a 200 mm Si wafer divided by the mass of source material loaded. The deposited mass was estimated by the film thickness and the film density i.e., density of Alq 3 = 1.55 gm / cm 3 . 15 M. A. Baldo, S. Lamansky, P. E. Burrows, M. E. Thompson, and S. R. Forrest, Appl. Phys. Lett. 75, 4 1999 . 16 S. R. Forrest, D. D. C. Bradley, and M. E. Thompson, Adv. Mater. 15 , 1043 2003 . 17 Comsol Multiphysics v 3.2. 18 M. Shtein, Ph.D. thesis, Princeton University, 2004. 19 R. Bird, W. Stewart, and E. Lightfoot, Transport Phenomena Wiley, New York, 2002 .

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